20

Unit - 2 Solutions .. ( Part - II )

Colligative properties: In dilute solutions, the properties which depend upon the no. of moles of
solute and not upon its nature are called as colligative properties.
Some of the colligative properties are :
1. Relative Lowering of vapour pressure 2. Osmotic Pressure
3. Elevation in boiling point. 4. Depression in Freezing point

These properties help in experimental determination of molar mass of solute, which is known
as observed molar mass. (or observed molecular mass). These properties are described below:

1. Relative Lowering of vapour pressure: The expression for Relative lowering of V.P. is as below:
When some non-volatile solute is added to a solvent, it results in lowering of vapour pressure.

According to Raoult’s law: ps = x1 p° …………………..(i)

where ps is V.P of solution , p° is the v.p of pure solvent and x1 is the mole fraction of solvent.

If x2 is the mole fraction of solute, then: x1 = 1 – x2 ( x1 + x2 = 1)

From eq.(i) , ps = (1 –x2) p°

ps po – ps
or = 1– x2 or = x2 …..…..(ii)
p po

From eq. (ii) , it is clear that, Relative lowering of V.P of a solution , containing non-volatile solute, is
equal to the mole fraction of solute.

p  – ps n2
Eq. (ii) can also be written as: = ………………(iii)
p 
n1 + n 2

where n1 and n2 are the no. of moles of solvent and solute respectively.
From the eqn.(iii), it is clear that relative lowering of vapour pressure depends upon the no. of
moles of solute. Hence it is a coligative property.

Determination of Molecular Mass: If w2 g of solute of mol. Mass M2 is dissolved in w1 g of solvent of

mol. mass M1, then eq.(iii) can be written as :

p –ps w 2 /M2
=
p w1 /M1 + w 2 /M2

If M1 is known, M2 can be calculated from this relation.

In case of dilute solution, n2 is very very small as compared to n1, thus, we can write eqn. (ii) as :

p  – ps n2 n2 w2
=  = M2
p 
n1 + n 2 n1 w1
M1
po – ps w 2 M1
or = , M2 can also be calculated from this relation.
po w1 M 2
 21

Numericals:

Q1. Vapour pressure of water at 293 K is 17.51 mm. The lowering of V.P of a sugar solution is
0.0614 mm. Calculate the mole fraction of water.
Sol. Vapour pressure of water p° = 17.51 mm
Lowering of vapour pressure (p° – ps) = 0.0614 mm
p – ps
By Raoult’s law, x2 = (mole fraction of solute)
p
0.0614
or x2 = = 0.00351
17.51
∴ Mole fraction of water x1 = 1– x2 = 1 – 0.00351 = 0.99649.

Q2. At 298 K , the vapour pressure of water is 23.75 mm Hg. Calculate the vapour pressure at
the same temp. over 5% aqueous solution of urea (NH2CONH2).

Sol. Here Weight of solution = 100 g

Wt. of solute , w2 = 5 g, ∴ wt. of solvent, w1 = 100 – 5 = 95 g
And Mol. mass of solute ( urea) M2 = 60; Mol. mass of solvent (water) M1 = 18

Vapour pressure of water p° = 23.75 mm

Vapour pressure of solution ps = ?

p – ps w 2 M1 23.75–ps 5  18
By Raoult’s law = or =
p w1 M2 23.75 95  60

or 23.75 – ps = 0.375 or ps = 23.375 mm

Q3. The V.P of 5% aqueous solution of a non-volatile organic substance at 373 K is 745 mm. Calculate
the Mol. mass of solute.
Hint: V.P of pure water at 373 K p° = 760 mm

ps = 745 mm , w2 = 5g, w1 = 95 g, M1 = 18, M2 = ? (Ans. 48)

Q4. The V.P of 2.1% of an aqueous solution of a non-electrolyte at 373 K is 755 mm. Calculate the Mol.
mass of solute. (Ans. 58.68)

Q5. How much Urea (Mol. mass = 60 g mol–1) should be dissolved in 50 g of water so that its vapour
pressure at room temp. is reduced by 25% . Calculate the molality of solution obtained.

By Raoult’s law p –ps w 2 /M2

Hint =
p w1 /M1 + w 2 /M2

The V.P is reduced by 25%, i.e if p° = 100 mm , then ps = 75 mm

w1 = 50, M1 = 18, M2 = 60 , solve and Find w2

100–75 w 2 /60 w 2 /60

= 0.25 =
100 50/18 + w 2 /60 , 2.78 + w 2 /60
22

We get, w2 = 55.6

Thus 55.6 of solute (urea) is present in 50.0 g of solvent (water),

w2 1000 55.6 1000

Therefore Molality = × = × = 18.53
M2 w1 60 50

Q6. The V.P of an aqueous solution of cane sugar ( Mol. mass = 342) is 756 mm at 373 K. How many grams
of sugar are present in 1000 g of water ?

Hint. By Raoult’s law p –ps w 2 /M2 760–756 w 2 /342

= =
p w1 /M1 + w 2 /M2 , 760 1000/18 + w 2 /342

On solving , we get w2 ≅ 100.5 g

Q7. The V.P of water at 293 K is 17 mm. Calculate the V.P of a solution containing 2 g of Urea (Mol. mass=
60) in 50 g of water. Assume that the solution is not dilute.

Hint: p° = 17 mm , w2 = 2g , w1 = 50 g , M2 = 60, M1 = 18 . Find ps (Ans. 16.8 )

Q8. The V.P of pure benzene at 25°C is 639.7 mm Hg and the V.P of a solution of non-volatile solute in
benzene at the same temp. is 631.9 mm Hg, calculate the mole fraction of solute and molality of
solution.
p – ps 639.7 – 631.9
Hint: Mole fraction of solute x2 = = = 0.0122
p 639.7

Mole fraction of solute × 1000

Molality of solution = (Note this formula)*
[Link] of solvent

Therefore m = 0.0122 × 1000 = 0.156 (Mol. Mass of C6H6 = 78)

78

Q9. V.P of an aqueous solution of glucose is 750 mm Hg at 373 K. Calculate the mole fraction of solute and
molality of solution. (Ans. x2 = 0.013 , m = 0.73)

n2
* As x2 = , for dilute solution n2 << n1
n1 + n 2
n w1
x2  n
2 n2 1000
= or n2 = x 2  or molality = x2 
1 w1 M1 M1
M1

2. Osmotic pressure: Important terms:

Semi permeable membrane: It is a membrane which allows only the solvent and not the solute
particles to pass through is called as semi permeable membrane.
These membranes are of two types:
(i) Natural Semi permeable membrane : obtained from plants or animals e.g. vegetable membrane
(ii) Artificial Semi permeable membrane: like cellophane or parchment paper.
 23

Diffusion: The phenomenon of movement of particles of a solute from a more concentrated to a less
concentrated solution so as to being about a uniform concentration throughout the bulk is known
as diffusion. { see fig. (i) }
Osmosis: The phenomenon of passage of pure solvent into a solution (or from a less concentrated to
a more concentrated solution) through a semi-permeable membrane is called as osmosis. fig.(ii)

Original level
H2O

Fig. (ii)→
KMnO4

Semi-permeable KMnO4
Fig. (i) ↑ Water solution
membrane

Note: The phenomenon of osmosis was observed first by Abbe Nollet in 1748
(In Greek , osmos = to push).

Difference between Osmosis and Diffusion

Osmosis Diffusion

1. In osmosis only the solvent molecules 1. In diffusion the solvent as well as

flow though semi per membrane. solute molecules move into each
other.
2. It takes place from lower conc. to higher 2. It takes place from higher conc. to
conc. lower conc.
3. A semi permeable membrane is used. 3. No semi permeable membrane is
used.
4. It takes place in solution only. 4. It takes place in gas as well in solution.
5. It can be stopped or reversed. 5. It cannot be stopped or reversed.

Demonstration of Osmosis: Let us take two eggs and remove their outer shells by dissolving them
in HCl. Place one egg in water and other in NaCl solution. The skin of egg acts as a semi-
permeable membrane. The first egg swells because pure water enters into the egg, whereas the
second egg shrinks because water comes out of the egg.

Normal size of egg (ii) Egg shrinks in salt solution

(i) Egg swells in water
24

Osmotic pressure: The minimum pressure which is applied on a solution to just prevent the entry of
pure solvent into the solution through semi- permeable membrane is known as Osmotic pressure.

Piston

Solution Solvent

Semi-permeable membrane

If pressure more than osmotic pressure is applied on the solution, the solvent will start flowing
from the solution into the pure solvent through semi permeable membrane. This process is known
as reverse osmosis. It can be used for desalination of sea water for getting drinking water.

Experimental Measurement of Osmotic pressure (Barkeley and Hartley ‘s method ) f. b.

Expression for Osmotic pressure: It is found that the osmotic pressure (P or π) of the solution is
directly proportional to the conc. (C) of the solution and its temp. (T)
Thus P ∝C and P∝T

or P ∝ CT or P =RCT
where R is a constant called as ‘solution constant’.
The above equation is written as P = C R T ……………..(i)
n
But C = , where n is the no. of moles of solute dissolved in V litre of the solution.
V
n
∴ eqn. (i) now becomes: P= RT ……….(ii)
V

or PV=nRT or 𝛑V=nRT
This is called as Van’t Hoff equation for dilute solution.
From eqn. (ii) it is clear that osmotic pressure, at any temp. T, is directly proportional to the no. of
moles of solute. Hence osmotic pressure is a colligative property.

Determination of Molecular Mass: if w g of solute of Mol. mass m is dissolved in V litre of the

solution then , eq (ii) becomes:
w wRT w
Thus PV = RT or P= (As no. of moles n= )
m mV m

wRT
or m=
PV

where R = 0.0821 litre atm deg–1mol–1 , P in atm. , V in litre

 25

Advantage of Osmotic pressure method: Osmotic pressure method is preferred for molecular
mass determination of proteins, polymers and other macromolecules. This is because, due to high
mol. masses, the changes observed in colligative properties are very small and very low osmotic
pressure can be easily measured in millimeter.
Elevation in boiling point method is not suitable because these biological molecules are not stable
at higher temp., whereas osmotic pressure is measured at room temp.

Isotonic solutions: The solutions which have same osmotic pressure at the same temp. are called
as isotonic solutions..
From equation P = CRT, we observe that the two isotonic solutions must have same molar conc.
If a solution has more osmotic pressure than the other, it is called as Hypertonic. If a solution
has less osmotic pressure than the other, it is called as Hypotonic.

Hemolysis and Plasmolysis: If an animal or plant cell is kept in contact with water then water will enter
into the cell through cell wall, causing swelling of the cell. This process is known as hemolysis. The
pressure developed inside the cell due to in flow of water into it is called turger.
If the cell is kept in contact with highly concentrated solution, then the cell would shrink as the
water comes out from the cell through the cell walls. This process is known as plasmolysis.

Biological Importance of Osmosis:

(i) Plants absorb water from the soil through their roots due to osmosis.
(ii) Movement of water into different parts of animal bodies and plants is also due to osmosis.
(iii) Osmosis also explains the stretching of leaves & flowers.
(iv) Bursting of red blood cells when placed in water is also due to osmosis.

Note: (i) A 0.91 % solution of pure NaCl is isotonic with human red blood corpuscles (RBC). Hence in this
solution RBC neither swell nor shrinks.
However a solution of NaCl with conc. less than 0.91 % is hypotonic. On placing RBC in this
solution, they will swell or burst due to hemolysis and if a solution of NaCl with conc. more than
0.91 % is hypertonic. On placing RBC in this solution, they will shrink due to plasmolysis.
(ii) Out flow of water from a cell is called as exo–osmosis whereas inflow of water is called as endo-
osmosis.
(iii) People taking a lot of salt develop swelling in their tissues, This disease is known as edma.
This is because of the retention of water in the tissue cells due to osmosis.
(iv) Preservation of meat by salting and that of fruits by adding sugar can be explained by
osmosis, This is because the bacteria which spoils them loses water in the salted meat or
candid fruits due to osmosis. As a result, it shrivels and dies.

Numericals :
n
Formulae : P = CRT (C in m/ℓ) Thus PV = RT or PV = nRT
V

w wRT wRT
PV = RT or P= or m=
m mV PV

where R = 0.0821 litre atm deg–1mol–1 , P in atm. , V in litre

If press. is in ‘bar’ then take R= 0.083 L bar K–1mol–1 ( 1 atm = 760 mm or torr )
26

1. Calculate the osmotic pressure of a solution containing 3.42 g of sucrose (C12H22O11) per
litre at 400 K.
Sol. Mol. mass of sucrose m = 342 , V = 1 litre , w = 3.42 g

wRT 3.42  0.0821  400

∴ P = = = 0.328 atm
mV 342  1

2. Calculate the osmotic pressure at 273 K of a 5% solution of Urea (Mol. mass= 60).

Sol. 5 % solution of Urea means 5 g of Urea is present in 100 ml of the solution

100
∴ w=5g, V = 100 ml = = = 0.1 litre
1000

R = 0.0821 lit atm deg–1mol–1 , T = 273 K

w RT 5  0.0821 273
P = = = 18.68 atm
mV 60  0.1

3. A 5% solution of cane sugar (Mol. mass = 342) is isotonic with 0.877 % solution of urea. Find
the mol. mass of urea.

Sol. Conc. of cane sugar = 5 g per 100 ml = 50 g per 1000 ml = 50 g/ℓ

50
∴ Molar conc. of cane sugar = m –1
342

and Conc. of urea solution = 0.877 g per 100 ml = 8.77 g per 100 ml = 8.77 g/ℓ

8.77 –1
= m ( if M is mol. mass of urea)
M
As the two solutions are isotonic, therefore their molar conc. will be same

8.77 50 342  8.77

= or M =  60
M 342 50

4. Calculate the osmotic pressure of a solution obtained by mixing 100 ml of 3.4 % of solution
of Urea (M.M. = 60) and 100 ml of 1.6 % solution of cane sugar ( M.M. = 342) at 293 K.
Sol. After mixing, the volume of solution = 200 ml
(i) Osmotic pressure of urea:
w = 3.4 g , V = 200 ml = 0.2 L , T = 293 K , M = 60

w RT 3.4  0.0821 293

P = = = 6.81 atm
mV 60  0.2

(ii) Osmotic pressure of cane sugar :

w = 1.6 g , V = 200 ml = 0.2 L , T = 293 K , M = 342

w RT 1.6  0.0821 293

P = = = 0.56 atm
mV 342  0.2

Total Osmotic pressure of solution = 6.81 + 0.56 = 7.37 atm

 27

5. Osmotic pressure of a solution containing 7 g of a protein per 100 ml of solution is 25 mm at

37°C. Calculate the mol. mass of protein.
100
Hint: w = 7g , T = 37 + 273 = 310 K, V= = 0.1 L
1000
P = 25 mm = 25 atm (1 atm = 760 mm) Find M (Ans. 54094)
760

6. The osmotic pressure of blood is 8.21 atm at 37°C. How much glucose should be used per
litre for an intravenous injection that is isotonic with blood?

Sol. P(blood) = P(glucose sol.) , P = 8.21 atm, V = 1.0 litre, M(for glucose) = 180, T = 37 + 273 = 310 K

w RT PV. m 8.21  1.0  180

P = or w = or w = = 58.06 g
mV RT 0.0821  310

7. The osmotic press. of solution containing 20 mg of insulin in 10 cm3 is 6.48 torr at 25 °C.
Calculate the molecular mass of insulin.
Hint : Here w = 20 mg = 20 × 10−3 g , R = 0.0821 L atm K–1 mol–1, T = 298 K ,

6.48 wRT
P = atm , V = 10 × 10–3 L, m= = 5739 g mol–1
760 PV

8. A 4 % solution of sucrose is isotonic with 3% solution of an unknown organic substance.

Calculate the mol. mass of unknown substance. (Ans. 256.5)

9. A solution of 10.2 g of glycerin per litre of a solution is found to isotonic with 2% solution of
glucose (Mol. mass = 180). Calculate the molar mass of glycerin. (Ans, 91.8)

10. Calculate the osmotic pressure of a solution obtained by mixing 100 cm3 of a 1.5 % sol. of urea
(Mol. mass = 60) and 100 cm3 of 3.42% solution of cane sugar (Mol. mass = 342) at 20°C.
(R = 0.0821 lit atm deg–1 mol–1). (Ans. P = 3.0 + 1.20 = 4.20 atm)

3. Elevation in Boiling Point:

Boiling Point: Boiling point of a liquid is the temp. at which its vapour pressure becomes equal to
the atmospheric press.
It is found that the vapour pressure of the solution
containing non-volatile solute, is always less than that of Atm. pressure
pure solvent. Hence the solution is to be heated more to
make its vapour pressure equal to the atmospheric
pressure. Thus boiling point of the solution is higher than
that of pure solvent.
V.P
At temp. T0, the V.P of a pure solvent becomes
equal to the atm. press. Therefore, T0 is the boiling point
of pure solvent and if T is the boiling point of the solution. ∆Tb

Then elevation (increases) in boiling point is equal to Temp. T0 T

T –T0 = ∆Tb (say)
Now, if ∆p is the corresponding lowering of V.P,
28

then ∆Tb ∝ ∆p
But according to Raoult;s Law:
∆p ∝ x2 (x2 is mole fraction of solute)

Thus ∆Tb ∝ x2

or ∆Tb = k. x2 ……..……(i)
(where k is a constant)

n2
∆Tb = k. where n1 & n2 are the no. of moles of solvent and solute respectively .
n1 + n 2

For dilution solution n2 < < n1 , ∴ n1 + n2 ≅ n1

n2 n2
∆Tb = k. ∆Tb = k.
n1 , w 1 /M 1

n2
∆Tb = k M1. ………………..(ii)
w1

n2
If w1 = 1 kg ( = 1000 g ) then: = m (molality of solution )
w1

Thus equation (ii) becomes : ∆Tb = k M1. m

Thus ΔTb = Kb . m , …………… (iii) (taking k.M1=Kb)

where Kb is called as molal elevation constant or ebullioscopic constant and m is molality of

solution.
if m = 1 then ΔTb = Kb,
Therefore, molal elevation constant may be defined as the elevation in boiling point when molality of
the solution is taken as unity.
From eqn. (ii) , it is clear that , the elevation in boiling point is directly proportional to the no. of
moles of solute. Hence, it is a colligative property.

Determination for Molecular mass: We have ΔTb = Kb . m

W2  1000
Molality of the solution is given as : m=
M2  W1

W2  1000 Kb  W2  1000
ΔTb = Kb  or M2 =
M2  W1 Tb  W1

Note : Unit of Kb = K/m = K Kg mol−1 ( as from eq.(iii) , Kb = ΔTb / m )

……………………………………………………………………………………………………………………………………………………………
 29

Numericals:

Q1. A solution of 12.5 g of a compound in 170 g of water gave a boiling point elevation of 0.63 K.
Calculate the mol. mass of compound, taking Kb = 0.52 K/M.

Sol . Here w2 = 12.5 g , w1 = 170 g

∆Tb = 0.63 , Kb = 0.52 K/M

Kb .w 2 .1000 0.52  12.5  1000

∴ M2 = = = 60.7
ΔTb .w1 0.63  170

Q2. The boiling point of water (100°C) becomes 100.52°C, if 3 g of a non volatile solute is dissolved
in 20 g of it. Calculate the molar mass of solute, Kb= 0.52 Km–1.

Ans. Elevation in boiling point , ΔTb = 100.52 – 100 = 0.52 °C

w1 = 20 g , w2 = 3 g , Kb = 0.52 K m–1

Kb  w2  1000 0.52  3  1000 = 150

M2 = =
Tb  w1 0.52  20
Q3. Find the boiling point of the solution obtained by dissolving 0.52 g of Glucose(C 6H12O6) in 80.2
g of water. Kb for water is 0.52 K/M.

Sol. Mass of solute w2 = 0.52 g Mol. mass of solute (Glucose) M2 = 180

Mass of solvent w1 = 80.2 g , Kb = 0.52 K/M

K b .w 2 .1000
ΔTb =
M2 .w 1

0.52  0.52  1000

= = 0.0187 K
180  80.2

Boiling point of solution T = T0 + ∆Tb = 373 + 0.0187 = 373.0187 K

(Boiling point of pure solvent i.e. water = 373 K)

Q4. On dissolving 3.24 g of sulphur in 40 g of benzene, boiling point of solution was higher than
that of benzene by 0.81 K, Kb for benzene is 2.53 K kg mol–1. What is the molecular formula of
sulphur ( At. Mass of S = 32) .
Sol. To find the mol. Mass of sulphur (Sn) , Mass of sulphur ( solute) w2 = 3.24 g

Mass of benzene ( solvent ) w1 = 40 g, Kb = 2.53, ∆Tb = 0.81

2.53  3.24  1000

∴ M2 = Kb  w2  1000 = = 253
Tb  w1 0.81  40
253
∴ n × atomic mass of S = 253 or n × 32 = 253 ∴ n= =8
32

∴ Molecular formula of sulphur = S8

Q5. 10 g of a non-volatile solute when dissolved in 100 g of benzene raise its boiling point by 1°. What is
the Mol. mass of solute ( Kb for benzene = 2.53 km–1) (Ans. 253)
30

Q6. A solution containg 12.5 g of non-electrolyte substance in 175 g of water gave boiling point
elevation of 0.70 K. calculate the molar mass of substance, K b for water is 0.52 k/m. (Ans. 53)

Q7. Calculate the molecular weight of a substance, 1.3 g of which when dissolved in 169 g of water gave
a solution boiling at 100.025°C at a pressure of one atm ( Kb = 0.52 km–1) (Ans. 160)

U. Kharbanda

4. Depression in freezing point: ( Cryoscopy ) :

The freezing point of a substance is the temp. at which the solid and liquid forms of a substance
are in equilibrium.
When some non volatile solute is added to the liquid, then the solid -liquid equilibrium will exist
at a temp. lower than the freezing point of pure solvent. As a result, the freezing point of the
solution is lowered, i.e there is depression in freezing point.
If T0 represents the freezing point of pure solvent and T represent the freezing point of solution.
Then Depression in freezing point : ΔTf = T0 –T
Now, if ∆p is the corresponding lowering of V.P,
then ∆Tf ∝ ∆p
But according to Raoult;s Law:
Liquid solvent
∆p ∝ x2
Vapour pressure

(x2 is mole fraction of solute) Solid solvent

Solution
Thus ∆Tf ∝ x2

or ∆Tf = k. x2 ……..……(i)
∆T
(where k is a constant) f

T T0
n2
∆Tf = k. Temp.
n1 + n 2

where n1 & n2 are the no. of moles of solvent and solute respectively.

For dilution solution n2 < < n1 , ∴ n1 + n2 ≅ n1

n2 n2
∆Tf = k. , ∆Tf = k.
n1 w 1 /M 1

n2
∆Tf = k M1. …………..(ii)
w1

n2
If w1 = 1 Kg ( 1000 g) then: = m (molality of solution)
w1

Then : ∆Tf = k M1. m

or ΔTf = Kf . m ( k M1 = Kf )

Here, Kf is called as Molal depression constant or Cryoscopic constant and m is molality of

solution.
If m = 1, then ΔTf = Kf.
Thus, molal depression constant may be defined as the depression in freezing point when molality
of the solution is taken as unity.
 31

The expression for Determination for Molecular mass is :

Kf  W2  1000
M2 =
Tf  W1
…………………………………………………………………………………………………………………………………………………………………………………………………………………………………..

Numericals:

1. A solution of 1.25 g of a certain non-electrolyte in 20.0 g of water freezes at 271.94 K.

Calculate the mol. mass of solute. Kf = 1.86 Km–1.
Sol. Here w2 = 1.25 g , w1 = 20.0 g , Kf = 1.86
∴ Freezing point of pure solvent ( water) = 273K
Freezing point of solution = 271.94 K
∴ Depression in freezing point , ∆Tf = 273 − 271.94 = 1.06 K

K f .w 2 .1000 1.86  1.25  1000

M2 = = = 109.7
ΔTf .w1 1.06  20

2. Normal freezing point of a solvent is 150℃. A 0.5 molal solution of urea in the above
solvent causes a freezing point depression of two degrees. Calculate the molal depression
constant.
Sol. Here molality , m = 0.5 , ∆Tf = 2°
ΔT f 2
As ∆Tf = Kf . m ; Kf = = = 4 Km –1
m 0.5

3. What mass of ethylene glycol ( molar mass = 62.0 g mol–1) must be added to 5.50 kg of water to
lower the freezing point of water from 0° to –10°C ? (Kf for water = 1.86 K Kg mol–1) .
( CBSE 2010 )
Sol. Here ∆Tf = 10°, w1 = 5.50 Kg = 5500 g

w2 = ΔTf . M2 . W1 10  62  5500
= = 1833.3 g = 1.833 kg
K f .1000 1.86  1000

4. An aqueous solution contains 5 % by mass of Urea and 10% by mass of Sucrose. If molal
depression constant of water is 1.86 k/m, calculate the freezing point of solution.
Sol. Here , Mass of solution = 100 g
Mass of solute , Sucrose = 10 g & Urea = 5 g
Mass of solvent ( water ) = 100 – ( 10 + 5) = 85 g ( w1)

5 10
Total no of moles of solute = 60
+ 342
= 0.112 mol

1000
∴ Molality = 0.112 × 85
= 1.31 m
∴ ∆Tf = Kf . m = 1.86 × 1.31 = 2.43 K
As, freezing point of pure solvent ( water) = 273 K
∴ Freezing point of solution = 273 – 2.43 = 270.57 K
32

5. A 5 % solution ( by mass ) of cane sugar in water has freezing point of 271 K. Calculate the
freezing point of a 5 % glucose in water if freezing point of pure water is 273.15 K. ( NCERT )

Hint: For 5 % solution (by mass) of cane sugar :

w2 = 5 g , w1 = 100− 5 = 95 g, m2 = 342 , Find Molality , m = 0.154
∆Tf = 273.15 − 271= 2.15° , As ∆Tf = Kf . m , Find Kf , Kf = 13.96

For 5 % solution of glucose :

w2 = 5 g , w1 = 100 − 5 = 95 g, m2 = 180 , Find Molality , m = 0.292

As ∆Tf = Kf . m or ∆Tf = 13.96 × 0.292 = 4.08 K

∴ Freezing point of glucose = 273.15 – 4.08 = 269.07 K

6. The normal freezing point of nitrobenzene is 278.82 K. A 0.25 molal solution of a certain non-volatile
solute in nitrobenzene causes a lowering of freezing point of nitrobenzene by 2°. Calculate the molal
depression constant ( Kf) (Ans. 8)

7. A solution containing 18 g of a non-volatile solute in 200 g of water freezes at 272.07 K. Calculate the
molecular mass of solute ( given Kf = 1.86 k/m) (Ans 180)

9. An aqueous solution contains 5% by wt of urea and 10% by weight of glucose. What will be its
freezing point . kf = 1.86 km–1 (Ans. 269.97 K)

19. 1.00 g of a non electrolyte solute dissolved in 50.0 g of benzene lowered the freezing point of
benzene by 0.40 K. The freezing point depression constant of benzene is 5.12 K kg mol –1. Fine the
Mol. mass of solute. (NCERT example) (Ans, 256 g mol–1) ( CBSE 2013 )

{[Link]}

Note : Different methods used for measurement of colligative properties are

1. Relative lowering of V.P by Ostward and Walker method
2. Osmotic Pressure by Berkeley and Hartley method
3. Elevation in [Link]. by Landsberger method
4. Depression in [Link] by Beckmann method

Abnormal Molecular Masses: When the molecular mass of a substance determined by studying any
of the colligative properties comes out to be different than the expected value, the substance is
then said to show abnormal molecular mass.
Abnormal mol. masses are observed when the solute undergoes dissociation or association in
the solution.
The electrolytes like NaCl, KCl etc. undergo dissociation in solution, thus the observed
molecular mass comes out to be less. e.g. NaCl dissociate in solution to give two ions (Na+ & Cl–)
. Therefore its observed mol. mass

=
1
2
(23 + 35.5) =
58.5
2
= 29.25

In case of solution of Carboxylic acid in benzene, the solute undergoes association in solution,
thus the observed molecular mass comes out to more than its calculated value. e.g. acetic acid ,
benzoic acid etc. when dissolved in Benzene exist as a dimer as shown:
 33

O H O

R C C R

O H O

Therefore its observed mol. mass of acetic acid (CH3COOH) = 2 × 60 = 120.

Van’t Hoff Factor: It is the ratio of experimental value of colligative property to the calculated value of
that property or ratio of calculated mol. mass to observed mol. mass i.e.

Observed value of colligative property

i=
Calculated value of colligative property

Calculated Molecular mass Mc

or i= =
Observed Molecular mass Mo
The value of i predicts the nature of solute in solution as below:
If i = 1 , the solute behaves normally in solution.
If i > 1 , the solute undergo dissociation in solution.
If i < 1 , the solute undergo association in solution.
e.g. for NaCl, KCl etc i = 2 and for acetic acid in benzene i = ½
For the solutions containing solute undergoing association or dissociation, the various expressions
for the colligative properties are modified as below:
Elevation in boiling point ∆Tb = i . Kb . m
Depression in freezing point ∆Tf = i . Kf . m
Osmotic pressure P = i C RT

Relation between Van’t Hoff factor and extent of Assciation or Dissociation of Electrolytes in solutions:
Using Van’t Hoff factor the extent ( or degree) of assciation or dissociation can be calculated as
below:
(a) Calculation of degree of association: It is defined as the fraction of the total substance which
exist in the form of associated molecules: i.e

[Link] moles associated

Degree of association ( α) =
Total [Link] moles taken

Suppose n molecules of solute A associate to form bigger molecule An i.e n A ⇋ An

If we start with one mole of A, Then at equilibrium:
No. of unassociated moles = 1– α
No. of associated moles = α/n
Total no. of moles = 1–α + α/n

1– α +α / n
Vant’ Haff factor i =
1

or i =1−α+α/n or 1− i = α − α/n

 n –1
or 1−i = α (1– 1/n) = α  
 n 
34

n Mc
or α = (1–i ) where i =
n –1 M0

( Percentage association = α × 100 )

(b) Calculation of degree of dissociation: it is defined as the fraction of total substance that
undergo dissociation
[Link] moles dissociated
i.e Degree of dissociation ( α) =
Total [Link] moles taken

Suppose, one molecule of the electrolyte (solute) dissociate to give n ions in solution.
If we start with one mole of electrolyte. Then at equilibrium:

No. of undissociated electrolyte = 1– α

No. of moles of ions formed =nα

Total no. of moles = 1– α + n α

1– α +n 
Vant’ Haff factor i =
1

or i = 1−α + n α = 1 + α (n −1)

or i −1 = α (n−1)

α =
( i – 1) Mc
or n–1 where i =
M0

( Percentage dissociation = α × 100 )

Numericals:

1. 0.1 mol of sugar was dissolved in 1 Kg of water. The freezing point of this solution was found to
be 272.814 K. What conclusion would you draw about the molecular state of sugar ? Kf for
water is 1.86 K kg mol–1.
Sol. Δ Tf (obs.) = 273 – 272.814 = 0.186 K
Molality = 0.1 m , Kf = 1.86
Δ Tf (cal.) = Kf . m = 1.86 × 0.1 = 0.186 K

As the experimentally observed value of colligative property is same as that of calculated value,
Therefore Mol. Mass is also the same ( i.e. 342)
Hence Molecular state of sugar remains unchanged in solution.

2. The freezing point depression of 0.1 m NaCl solution is 0.372°C. What conclusion would you
draw about its molecular state? Kf for water is 1.86 k/m.
Sol. Here Δ Tf (obs.) = 0.372 K

And Δ Tf (cal.) = Kf . m = 1.86 × 0.1 = 0.186 K

 35

As the experimentally observed value of colligative property comes out to more than the
calculated value, This shows that the solute ( NaCl) undergoes dissociation in solution.

Δ Tf (obs.) 0.372
∴ Van’t Hoff factor i = Δ Tf (cal.)
= 0.186
= 2

It means that each NaCl molecule dissociates to give two particles, (NaCl Na+ + Cl–)

3. The freezing point depression of 0.1 molal solution of acetic acid in benzene is 0.256 K. K f for
benzene is 5.12 Kkg mol–1. What conclusion can you draw about the molecular state of acetic acid?

Sol. Here Δ Tf (obs.) = 0.256 K

And Δ Tf (cal.) = Kf . m = 5.012 × 0.1 = 0.512 K

Δ Tf (obs.) 0.256 1
Therefore ί = = =
Δ Tf (cal.) 0.512 2

As the experimentally observed value of colligative property is half of the calculated value,
therefore Mol. mass (observed) will be double of the calculated value, which shows that acetic
acid exist as a ‘dimer’ in the solution of benzene i.e. as (CH3COOH)2.

4. The freezing point of a solution containing 0.3 g of acetic acid in 30.0 g of Benzene is lowered by
0.45°C. Calculate Van’t Hoff factor. Kf for benzene is 5.12 K kg mol–1.

Δ Tf (obs.) 0.45
Hint: ί = = = 0. 527
Δ Tf (cal.) 0.853

5. Which of the following solution will have the highest and which will have the lowest freezing point
and why? (i) 0.1 M NaCl solution (ii) 0.1 M Glucose solution (iii) 0.1 M BaCl 2 solution.
Ans. Glucose does not dissociate, NaCl dissociate to give two ions and BaCl2 dissociate to give three
ions, therefore depression in freezing point will be maximum in BaCl2 and minimum for glucose
solution. Hence, lowest freezing point will be of BaCl2 and highest freezing point will be of
Glucose solution.

6. Arrange the following solution in increasing order of their osmotic pressure:

(a) 34.2 g/ℓ Sucrose (b) 60 g/ℓ Urea
(c) 90.0 g/ℓ Glucose (d) 58.5 g/ℓ Sodium Chloride
Give reason in support of your answer.
34.2
Ans. (a) 34.2 g / ℓ Sucrose ( C12H22O11 ) = = 0.1 M
342

60
(b) 60 g / ℓ Urea (NH2CONH2) = = 1M
60

90
(c) 90.0 g / ℓ Glucose (C6H12O6) = = 0.5 M
180

58.5
(d) 58.5 g / ℓ Sodium Chloride (NaCl) = = 1 M = 2 M (after dissociation)
58.5
As Osmotic pressure depends upon molar conc, therefore the order is :
Sucrose < Glucose < Urea < NaCl

7. Calculated the amount of KCl which must be added to 1 kg of water so that the freezing point is
depressed by 3 K, Kf for water is 1.86 C/m.

Sol. Here ΔTf = 3 K, Kf =1.86 C/m

36

As KCl dissociates in solution to give two ions:

2
KCl K+ + Cl– therefore ί = =2
1

As ΔTf = ί . Kf . m
3
or 3 = 2 × 1.86 x m therefore m = = 0.806
2 × 1.86

Hence, amount of KCl to be dissolved in 1 Kg of water = 0.806 mol.

1mole of KCl = 74.5 g [ Mol. mass of KCl = 39 + 35.5 = 74.5 ]

0.806 mole of KCl = 74.5 x 0.806 = 60.047 g.

8. Calculate the amount of NaCl which must be added to 100 g of water so that the freezing point is
depressed by 2 K. For water Kf = 1.86 K/m. (Ans. 3.147 g )

Hint: As ΔTf = ί . Kf . m or 2 = 2 × 1.86 × m , m = 0.538

Mol. Mass of NaCl = 58.5
Amount of NaCl to be dissolved in 1000 g of water = 0.538 × 58.5 = 31.47 g

9. What mass of NaCl (molar mass = 58.5 g mol–1) must be dissolved in 65 g of water to lower the
freezing point by 7.5°C? . The freezing point depression constant Kf , for water is 1.86 K kg mol–1.
Assume Van’t Hoff factor for NaCl is 1.87. (CBSE 2010)

Hint: As ΔTf = ί . Kf . m
or 7.5 = 1.87 × 1.86 × m or m = 2.156

∴ Amount of NaCl to be dissolved in 1000 g of water = 2.156 × 58.5 = 126.126 g

126.126
Thus Amount of NaCl to be dissolved in 65 g of water = × 65 = 8.2 g.
1000

10. Determine the osmotic pressure of a solution prepared by dissolving 2.5 × 10−2 g of K2SO4 in 2 L of
water at 25 C , assuming that it is completely dissociated. ( molar mass of K 2SO4 = 174 g mol−1 )

2.5 × 10−2
Hint : P = i CRT , Here i = 3 , C ( in mol L−1 ) = = 7.18 × 10−5 mol L−1
174 × 2
( Ans. 0.00527 atm )

Note : (i) Brass is homogeneous mixture of Cu & Zn, Bronze is homogeneous mixture of Cu & Sn
and German silver is that of Cu, Zn & Ni.
(ii) 1 ppm of F− ions in water prevents tooth decay, 1.5 ppm causes teeth to become coloured
and higher conc. of F− ions can be used as poison, e.g. Sodium fluoride for killing rats.

U. Kharbanda
 37

Conceptual Questions
Q1. Give an example of a solution containing a liquid solute in a solid solvent.
Ans. Hydrated salts like CuSO4 . 5 H2O.
Q2. Why liquid ammonia bottle is first cooled in ice before opening it?
Ans. At room temp., the vapour pressure of liquid ammonia is very high. On cooling, vapour pressure
decreases. Hence, the liquid ammonia will not splash out.
Q3. Why does the use of pressure cooker reduce cooking time?
Ans. The weight over the lid does not allow the steam to go out. As a result, pressure inside the cooker is
high. Higher the external pressure, higher is the boiling point and faster is the cooking.
Q4. What is relation between normality and molarity of a given solution of H2SO4?
Ans. Normality = 2 × Molarity.
Q5. Two liquid A and B on mixing produce a warm solution. Which type of deviation from Raoult’s
law does it show?
Ans. The solution shows a negative deviation.
Q6. What role does the molecular interaction play in solution of alcohol and water? (NCERT )
Ans. There is strong hydrogen bonding in alcohol molecules as well as water molecules. On mixing, the
molecular interactions are weaken. Hence, they show positive deviations from ideal behaviour.

Q7. What is the effect of temperature on molarity of a solution?

Ans. Molarity decreases because volume of the solution increases with increases in temp. but no. of mole
of solute remain the same.
Q8. Why it is advice to add ethylene glycol to water in a car radiator while driving in a hill station?
Ans. It is done to lower the freezing point of water so that it does not freeze.
Q9. Sodium chloride is used to clear snow from the roads. Why?
Ans. Sodium chloride depresses the freezing point of water to such an extent that it cannot freeze to form
ice. Hence it melts off easily.
Q10. 10cc of a liquid A were mixed with 10cc of liquid B. The volume of the resulting solution was
found to be 19.9cc. What do you conclude?
Ans. Decrease in volume means stronger intermolecular forces of attraction on mixing. Hence the solution
will show a negative deviation from Raoult’s law.
Q11. What are isotonic solutions? Give one example.
Ans. Solutions having equal osmotic pressure. e.g. 0.1 M glucose and 0.1 M sucrose solutions.
[Link] much mol. mass of NaCl is obtained experimentally using colligative properties?
Ans. NaCl dissociate to give two ions, therefore no. of particles will become double and mol. mass will be
half of the calculated value.
i.e. ½ ( 23 + 35.5) = ½ (58.5) = 29.25
Q13. How is colligative property of solution changed when a solute in a solution undergoes
(i) association (ii) dissociation?
Ans. (i) The value of colligative property decreases. (ii) The value of colligative property increases.
Q14. Oil and water do not mix .Why?
Ans. Oil is non-polar whereas water is polar.
Q15. What is the effect of temperature on the solubility of sodium sulphate decahydrate?
Ans. The solubility first increases upto 32.4°C ( called transition temp.) and then decreases.
38

Q16. Why do gases nearly always tend to be less soluble in liquid as the temperature is raised?
( NCERT)
Ans. Dissolution of gas in liquid is an exothermic process. As the temp. is increased, equilibrium shifts in
the backward direction and therefore, the solubility decreases.
Q17. Why a person suffering from high blood pressure is advised to take minimum quantity of
common salt?
Ans. As osmotic pressure is directly proportional to the conc. of solute, therefore on taking large amount
of common salt, Na+ & Cl– on conc. in body fluid increases & thus conc. of solute increases, As a result
osmotic pressure increases which may rupture the blood cells.
Q18. What do you expect to happen when Red Blood Corpuscles (RBC’s) are placed in:
(i) 1.5% NaCl solution (ii) 0.5% NaCl solution ?
Ans. (i) They will shrink due to plasmolysis (ii) They will swell due to hemolysis.
This is because RBC’s are isotonic with 0.9% NaCl solution.
Q19. Why Camphor is used as a solvent for finding molecular masses of organic compounds like
naphthalene or anthracene.
Ans. Camphor has high molar depression constant. Therefore it is used as a solvent for finding molecular
masses of organic compounds like naphthalene, anthracene etc. which are soluble in camphor in
molten state. The depression in melting point (or depression in freezing point) is so large that it can
be found using ordinary thermometer. (This is called as Rast method ).
Q20. Why boiling point of water is increased on addition of sodium chloride into it?
Ans. When NaCl is dissolved in water, vapour pressure of water decreases therefore the solution has to be
heated more to make vapour pressure equal to the external pressure, hence the boiling point is
increased.
Q21. What is de-icing agent? How does it work?
Ans. Common salt is called de-icing agent because it lowers the freezing point of water to such an extent
that it does not freeze to form ice. Hence, it is used to clear snow from roads.
Q22. Why do aquatic species like fish feel more comfortable in lakes in winter than in summer ?
Ans. Aquatic species need dissolved oxygen for breathing. As solubility of gases decreases with the
increase of temp., thus less oxygen is available in summer in lakes. Hence they feel more
comfortable in winter because solubility of oxygen is higher at low temp.
Q23. Why pure ethyl alcohol cannot be obtained from rectified spirit ( 95.6 % alcohol ) even by
fractional distillation ?
Ans. This is because a mixture of 95.6 % alcohol with 4.4 % water forms an azeotrope i.e. a constant
boiling mixture.
( U. Kharbanda )
 39

Additional Numericals :

1. The vapour pressure of pure benzene at a certain temp. is 0.850 bar. A non-volatile, non-electrolyte
solid weighing 0.5 g is added to 39.0 g of benzene ( molar mass 78 g mol –1). The vapour pressure of
the solution then is 0.845 bar. What is the molar mass of the solid substance? ( NCERT Example )

2. 200 cm3 of an aqueous solution of a protein contains 1.26 g of protein. The osmotic pressure of this
solution at 300 K is found to be 2.57 × 10–3 bar. Calculate the molar mass of the protein.
( NCERT Example )
( w2 = 1.26 g , V = 0.2 L , take R = 0.083 L bar K–1 mol–1, find M2 )
3. The boiling point of benzene is 353.23 K. When 1.80 g of a non-volatile solute was dissolved in 90 g of
benzene, the boiling point is raised to 354.11 K. Calculate the molar mass of the solute. Kb for benzene
is 2.53 K kg mol–1. ( NCERT Example )

4. 18 g of glucose, C6H12O6 is dissolved in 1 kg of water in a saucepan. At what temp. will the water boil
at 1.013 bar pressure ? Kb for water is 0.52 K kg mol–1 . ( NCERT Example )

{at 1.013 bar pressure, water boils at 373.15 K temp (To). Find boiling point of solution T = To+∆Tb }

5. 45 g of ethylene glycol (C2H6O2) is mixed with 600 g water. Calculate (a) freezing point depression
(b) freezing point of solution. Kf for water is 1.86 K kg mol–1 . ( NCERT Example )

6 . 2.0 g of Benzoic acid dissolved in 25.0 g of benzene shows a depression in freezing point equal to
1.62 K. Molal depression constant ( Kf) of benzene is 4.9 K Kg mol −1 . What is the percentage
association of the acid if it forms dimer in the solution ? ( NCERT Example )

Hint : w2 = 2.0 g , ∆Tf (obs.) = 1.62 K , Kf = 4.9 K kg mol–1 , Find M2 , M2(obs.) = 242 g mol–1
M2(Calculated) for Benzoic acid ( C6H5COOH ) = 72 + 5 + 12 + 16 + 16 + 1 = 122 g mol–1

Mc 122 n
i= = = 0.504 , for association α = (1− i ) , ( for dimerisation n =2 ) , Find α
Mo 242 n −1

Percentage association = α × 100

Answers: 1. 170 g mol–1. 2. 61039 g mol–1. 3. Ans. 58 g mol–1. 4. Ans. 373.202 K.

5. Ans. 2.25 K, 270.75 K. 6. 99.2 %

U. Kharbanda
40

Assignment

1. Give an example of each : (i) Solid in solid solution (ii) Liquid in solid solution
2. Find the strength of 0.01 molar sugar solution in water.
3. What is the molarity of 0.5 N H2SO4 solution?
4. Explain the effect of temp. and pressure on the solubility of a gas in liquid?
5. What is transition temp.?
6. Define the molarity and molality. Why molality is preferred to molarity?
7. Which of the following are not affected by temp. : molarity, normality, molality and mole fraction .
Give reason.
8. State and explain Henry’s law. What are its limitations?
9. What is the effect of temp. on the value of Henry’s constant?
10. What is the cause of dissolution of NaCl in water?
11. Define vapour pressure of a liquid. Explain the effect of addition of non-volatile solute to liquid on
its vapour pressure.
12. Give the example of each: (i) substitution solid solution (ii) Interstitial solid solution.
13. What are ideal solutions? What types of solutions are generally ideal?
14. What is non-ideal solution. What types of deviations from ideal behavior are shown by mixture of

(i) ethanol and cyclohexnae (ii) chloroform and acetone? Give reason for such deviations.

15. What is the sign ∆H and ∆V for non-ideal solution showing (i) positive deviation (ii) negative
deviation? Explain.
16. Which colligative property is preferred for molar mass determination of macromolecules and why?
17. A known weight of non –volatile solute is dissolved in a given amount of solvent. Explain how
Raoult’s law can be used to determine the molecular weight of this solute.
18. Define boiling point. Why the boiling point of a liquid increases on addition of non volatile solute
into it.
19. What is meant by depression in freezing point. Explain how this property can be used to determine
the molar mass of a non- volatile solute.
20. Why some substances show abnormal molecular masses. Explain with suitable examples.
21. What is Van’t Hoff factor? What happens when its value is not equal to one?

22. Differentiate between molarity and molality values for a solution. What is the effect of
change in temp. on molarity and molality values ? (CBSE 2011)
23. State the following: (i) Raoult’s law in its general form in reference to solutions.
(ii) Henry’s law about partial pressure of a gas in a mixture. (CBSE 2011)

U. Kharbanda